Indolenine dyestuffs

ABSTRACT

The dyestuffs are used for dyeing and printing natural and synthetic materials.   AND THEIR USE AS COUPLING OR CONDENSATION COMPONENTS FOR THE MANUFACTURE OF BASIC INDOLENINE DYESTUFFS OF THE FORMULA   Dihydroindoles of the formula

United States Patent 11 1 Schmitt 1 1 Jan. 14, 1975 I INDOLENINEDYESTUFFS [75] Inventor: Ernst Schmitt, Cologne, Germany BayerAktiengesellschait, Lcverkuscn, Germany 122 Filed: Dec. 9, 1971 1211Appl. No.: 206,537

[73] Assignce:

[30] Foreign Application Priority Data Dec. 9, 1970 Germany 1. 2060614152 US. c1 260/240 G, 8/3, 8/12, 8/542, 8/177 R, 8/178 R, 8/178 E,106/22,

162/162, 260/37 R, 260/40 TN, 260/240 1),

260/307 F, 260/348 R, 260/326 N, 260/319.1,

- OTHER PUBLICATIONS CA. 51: 1595lh (1957) Cerniani et al.

Primary Examiner-Henry R. Jiles Assistant ExaminerS. D. WintersAttorney, Agent, or Firm-Plumley & Tyner [57] ABSTRACT Dihydroindolcs ofthe formula RE I l R2 3 CH 1 R -CH-1JH R and their use as coupling orcondensation components for the manufacture of basic indoleninedyestuffs of the formula i l3] B The dyestuffs are used for dyeing andprinting natural and synthetic materials.

8 Claims, No Drawings INDOLENINE DYESTUFFS I R4-CH-CHR wherein Rrepresents a lower alkyl radical and R represents a lower alkyl radical,and the radicals R and R together with the shared C atom of thedihydroindole ring can form a saturated 5- membered or 6-membered ring,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5- membered or 6-membered ring whichoptionally possesses non-ionic substituents, or represents one or morecarboxy radicals,

R denotes hydrogen or a non-ionic substituent and R denotes hydrogen ora non-ionic substituent, and a process for their manufacture.

A further subject of the invention are mixtures these heterocycliccompounds.

The invention also relates to the use of oxazoloindoles as couplingcomponents or condensation components for the manufacture of basicdyestuffs.

A further subject of the invention are basic dyestuffs of the formula Rrepresents a lower alkyl radical and R represents a lower alkyl radical,and the radicals R and R together with the shared C atom oftheindolenine ring can form a saturated S-membered or 6-membered ring,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused membered or 6-membered ring which optionally Zrepresents the remaining part of a S-membered or 6-membered ring towhich further rings can be fused,

D represents a carbocyclic or heterocyclic ring with cyclic, planar(4n+2)-n--electron arrangement, to which further rings can be fused, and

X represents an anion, which can be manufactured from9a-methyl-2,3,9,9atetrahydrooxazolo-[3,2a]-indoles.

The invention also relates to mixtures of such basic dyestuffs. Afurther subject of the invention is the use of these basic dyestuffs fordyeing and printing natural and synthetic materials.

Non-ionic substituents are, for example, alkyl radicals which accordingto the invention can be cyclic or acyclic, branched or straight-chain,substituted and unsubstituted, such as methyl, ethyl, n-propyl, n-butyl,

' series,

possesses non-ionic substituents, or represents one or more carboxyradicals,

R, denotes hydrogen or anon-ionic substituent,

R denotes hydrogen or a non-ionic substituent and R denotes a loweralkyl or aralkyl radical, Ar represents an aromatic or hetero-aromaticradical which contains at least one donor group which is conjugated withthe methine bridge,

iso-butyl, tert.-butyl, cyclohexyl, and also higher alkyl radicals, suchas n-C H and their substitution products, such as chloromethyl,methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl,nhexyloxymethyl, n-octyloxymethyl, n-nonyloxymethyl, n-dodecyloxymethyl,aryloxymethyl, such as phenoxymethyl, p-nitrophenoxymethyl,p-methoxyphenoxymethyl and p-chlorophenoxymethyl, B-methoxyethyl,fluorine, chlorine, nitrile, ,B-cyanoethyl, trifluoromethyl, arylradicals, especially those of the benzene such as phenyl,Z-methylphenyl, '3- methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl,2-chlorophenyl, 4chlorophenyl, 2-methyl-4- chlorophenyl, 4-cyanophenyl,4-nitrophenyl, 4- methoxyphenyl and 4-methylsulphophenyl, aralkylradicals, especially benzyl and its homologues and their substitutionproducts, such as 4-methylbenzyl, 4- chlorobenzyl, 4-nitrobenzyl,4-methoxybenzyl and 2- phenylethyl, alkoxy radicals, such as methoxy,ethoxy, n-propoxy and n-butoxy, sulphamoyl radicals, nitrile groups,carboalkoxy radicals, such as carbomethoxy and carboethoxy, andcarboaryloxy radicals, such as carbophenoxy and 4-methylcarbophenoxy,and also alkenoxymethyl, such as allyloxymethyl, as well asalkinoxymethyl, such as propargyloxymethyl.

Lower alkyl radicals are those with 1 4 carbon atoms, such as methyl,ethyl, n-propyl, iso-propyl, nbutyl, isobutyl, tert.-butyl and theirsubstitution prod ucts, such as chloromethyl, trifluoromethyl,B-chloroethyl, B-methoxyethyl, B-cyanoethyl and B-dimethylaminoethyl.

Suitablelower alkenyl radicals are, for example: propen-(2)-yl-l,buten-(3)-yl-2 and 2-methylene-propyl-l.

Aralkyl radicals according to the invention are, for example, benzyl,B-phenylethyl, y-phenylpropyl, phenylpropyl-(2,2), 4-methylbenzyl,4-chlorobenzyl and 4-nitrobenzyl.

Possible anionic radicals A are the organic and inorganic anions whichare customary for basic dyestuffs and as examples there may bementioned: chloride, bromide, iodide, carbonate, bicarbonate, CH SO{, Cl-l SOf, p-toluenesulphonate, H50 S0 disulphate, aminosulphate,methanesulphonate, benzenesulphonate, p-chlorobenzenesulphonate, phosphomolybdate, phosphotungstate, acetate, benzoate, chloroacetate,formate, propionate, lactate, crotonate, N0 perchlorate, ZnCl the anionsof saturated or unsaturatedaliphatic dicarboxylic acids, such as malonicacid, maleic acid, tartaric acid, citric acid, oxalic acid, itaconicacid, succinic acid, glutaric acid, adipic acid, pimelic acid andsuberic acid, and alkanesulphonic acid radicals, such asn-dodecylsulphonic acid, tetrapropylenesulphonic acids, C, Calkanesulphonic acid mixtures and ligninsulphonic acids.

Colourless anions are preferred; for dyeing from an aqueous medium,those anions which do not excessively impair the solubility of thedyestuff in water are preferred.

For dyeing from organic solvents, those anions are also frequentlypreferred which assist the solubility of the dyestuff in organicsolvents or at least do not affect it adversely, such as anions ofmonobasic organic acids with 4-30 carbon atoms.

Preferred oxazoloindoles of the formula (I) are those of the formula(III) 3 was N (III) R ':H-ba- R5 wherein R represents methyl, ethyl orn-propyl, R represents methyl, ethyl or n-propyl, R represents hydrogen,one or more identical or different radicals from amongst fluorine,chlorine,

methyl, ethyl, n-propyl, trifiuoromethyl, tert.-butyl,

n-hexyl, n-dodecyl, cyclohexyl, phenyl, 4- nitrophenyl, 4-methoxyphenyl,benzyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylmercapto,

ethylmercapto, methylsulphonyl, acetamino, phenoxy, carbomethoxy,carboethoxy, carbophenoxy, sulphamoyl, nitrile or carboxyl, and

R and R independently of one another represent hydrogen, -methyl, ethyl,n-propyl, n-butyl, n-

pentyl, n-hexyl, n-nonyl, chloromethyl, methoxymethyl, ethoxymethyl,n-propoxymethyl, nbutoxymethyl, n-hexyloxymethyl, noctyloxymethyl,n-nonyloxymethyl, ndodecyloxymethyl, phenoxymethyl, phenyl, 4-

chlorophenyl, 4-nitrophenyl, 4-methoxyphenyl, carbomethoxy, carboethoxy,carbophenoxy, allyloxymethyl, chlorine or nitrile. Particularlypreferred compounds (I) and (III) are those wherein R and R or R and Rrepresent hydrogen or one of the radicals R and R or R and R representshydrogen and the other represents a methyl radical, a chloromethylradical, a phenyl radical, a phenoxymethyl radical, a methoxymethylradical, an allyloxymethyl radical or a n-hexoxymethyl radical. Foreconomic reasons, particularly interesting compounds of the formulae (I)and (III) are those, wherein R and R or R and R represent hydrogen, orone of the radicals R, and R or R, and R represents methyl. Compounds ofthe formulae (I) and (III) in which R and R or R, and R representhydrogen, are of outstanding importance. When using unsymmetricaloxiranes, that is to say those oxiranes in which the radicals R and R orR and R are different, oxazoloindole mixtures can be produced.

The conversion of indolenines into indolenium salts by means ofalkylating agents, such as dimethyl sulphate and methyl iodide hasalready been known for a long time. Furthermore, the reaction of 2,3,3-trimethyl-indolenine with 2-bromoethanol to give N-(2-hydroxyethyl)-2,3,3-trimethyl-3-H-indoleninium bromide is known fromBelgian Patent Specification No. 726,639. Furthermore, the use oflhydroxyethy- 1-3,3-dimethyI-Z-methyIene-indoline and of thecorresponding 1-hydroxypropyl and lhydroxybutyl compounds as couplingcomponents of basic dyestuffs is known in Belgian Patent Specification726,639.

It has now been found that, surprisingly, the alkylating reaction ofindolenines of the formula 5 M- CH (Iv) wherein R represents a loweralkyl radical and I o R 4 ca ca R (v) wherein R denotes hydrogen or anon-ionic substituent and R denotes hydrogen or a non-ionic substituent,leads simply, and in part with excellent yields, to oxazoloindoles ofthe formula (I).

The reaction can be carried out in bulk or in the pres ence ofsubstances which react acid or alkaline, with or without the addition ofwater. Instead of water, organic solvents can also be used; at times itis useful to use a mixture of water and one or more organic solvents.

Organic acids which are suitable according to the invention are, forexample, formic acid, acetic acid, propionic acid, monochloroacetic anddichloroacetic acid,

B-chloropropionic acid, succinic acid, benzoic acidandp-toluene-sulphonic acid. Organic and inorganic acids can also beused as mixtures; in this case, aqueous hydrochloric acid, sulphuricacid, nitric acid or phosphoric acid are particularly suitable.

Possible substances which give an acid reaction are also Lewis acids,such as ZnCI SnCl AlCl BE, and FeCl;,, which are preferably usedtogether with organic acids, for example those from post-sulphonatedstyrene-divinylbenzene copolymers.

As organic solvents, the following can, for example, be used: methanol,ethanol, ethylene glycol, benzyl alcohol, acetone, isopropyl methylketone, methyl ethyl ketone, cyclohexanol,tetrahydrofurane, dioxane,ethyl acetate, phthalic acid diethyl ester, phthalic acid n-.

l-chloro-2,3-epoxypropane,

propyl' ester, cyclohexane, cyclohexene, benzene, xylenes, chlorobenzeneor ethylene chloride.

The reaction is preferably carried out in acetic acid and particularlypreferably in acetic acid-water mixtures.

The reaction can be carried out at temperatures between about -C and+180C, preferably at temperatures between C and 80C. Especially in thecase of low-boiling oxiranes, such as ethylene oxide, propylene oxide,butylene-( l ,2) oxide and l-chloro-2,3- epoxypropane, the reaction canadvantageously be carried out under pressure.

From amongst the long series of the indolenines which are suitableaccording to the invention, the following may be mentioned as aselection.

Table 1 2,3,3-Trimethyl-indolenine, 2-methyl-3,3- diethylindolenine,2,3,3,S-tetramethylindoleine, 2,3,3- trimethyl-S-chloro-indolenine,2,3,3-trimethyl-5- carboxy-indolenine, 2,3,3-trimethyl-5-cyclohexylindolenine, 2,3,3,7-tetramethyl-5-cyclohexylindolenine,2,3,3-trimethyl-5-trifluoromethylindolenine,2,3,3-trimethyl-5-methoxyindolenine, 2,3,3-trimethyl-S-sulphamoylindolenine, 2,3,3-trimethyl-5-phthalimidomethyl-indolenine, 2,5-dimethyl-3,3- diethylindolenine,2-methyl-5-chloro-3,3- diethylindolenine,2,3,3-trimethyl-5,6-benzoindolenine, 2,3,3-trimethyl-5-ethoxyindolenine,2,3,3- trimethyl-S-butoxyindolenine, 2-methyl-3,3-diethyl-5-methoxyindolenine, 2-methyl-3,3-diethyl-5-carboxyindolenine,2-methyl-3,3-diethyl-S-carbomethoxyindole- Table 2 Oxiranes which aresuitable according to the invention are, for example: ethylene oxide,propylene oxide,

butylene-( 1,2) oxide, butylene-(2,3) oxide,

epoxypropane, l-ethoxy-2,3-epoxypropane, l-n-propoxy-2,3-epoxypropane,l-isopropoxyepoxypropane, l-n-butoxy-2,3-epoxypropane,l-isobutoxy-2,3-epoxypropane, l-tert.-butoxy-2,3- epoxypropane,l-n-pentoxy-2,3-epoxypropane, lisopentoxy-2 ,3-epoxypropane, -hex0xy- 1-n-heroxy- 2,3-epoxypropane, l-(2'-ethyl-n-hexoxy)-2,3- epoxypropane,l-n-octyloxy-2,3-epoxypropane, l-nnonyloxy-2,3-epoxypropane,l-n-decyloxy-2,3-

2-methyl-3,3-diethyl-5-' l-methoxy-2,3-

epoxypropane, l-n-undecyloxy-2,3-epoxypropane, 1-n-dodecyloxy-2,3-epoxypropane, l-n-hexadecyloxy- 2,3-epoxypropane,l-n-octadecyl-2,3-epoxypropane, 1-dimethylamino-2,3-epoxypropane,l-diethylamino- 2,3-epoxypropane, l-di-n-butylamino-2,3-

epoxypropane, l-phenoxy-2,3-epoxypropane,l-(pnitrophenoxy)-2,3-epoxypropane, l-(pmethylphenoxy)-2,3-epoxypropane, l-(m methylphenoxy)-2,3-epoxypropane,l-( omethylphenoxy )-2,3-epoxypropane, l-(nonylphenoxy)-2,3-epoxypropane, l-

(dodecylphenoxy)-2,3-epoxypropane, styrene oxide,allyloxy-2,3-epoxypropane, propargyloxy-2,3- epoxypropane,2,3-epoxypropanol-( l 1,2- epoxydecane,l,2-epoxy-3-(4-methylphenyl-mercapto)-propane, benzoic acid-2,3-epoxypropyl ester, N- (2,3-epoxypropyl)-pyrrolidine, 3-(diallylamino)-l,2-epoxypropane, 3,3,3-trichloro-1,2-epoxypropane, 3,3,- 3-trifluoro-l,2-epoxypropane, 3,4-epoxybutene-( l l,2-epoxy-3-(4-methylphenyl)-propane and 1,2-epoxy- 3-(4-methoxyphenyl)-propane.

Ethylene oxide, propylene oxide, allyloxy-2,3-

epoxypropane and phenoxy-2,3-epoxypropane are preferred, and ethyleneoxide is particularly preferred.

Surprisingly, oxazoloindolesare suitable condensation components for themanufacture of methine dyestuffs. Furthermore, the oxazoloindoles are,surprisingly, suitable for use as coupling components for themanufacture of hydrazone dyestuffs.

The oxazolo-[3,2a]-indoles obtainable according to the invention canhere not only be reacted after prior purification to give methine .andhydrazone dyestuffs, but can also be reacted directly from the reactionmixture or after simple removal of the diluent.

When the crude product is used for the manufacture of basic dyestuffs inaccordance with the invention, it is of advantage to manufacture thecrude product in media containing formic acid or acetic acid, especiallyif ethylene oxide or propylene oxide are employed.

Methine dyestuffs according to the invention, of the general formula HH=CH- Ar (v1) I E 4 cnorm wherein Ar represents an aromatic, carbocyclicradical which contains at least one donor group conjugated with themethine bridge,

R represents a lower alkyl radical and R represents a loweralkylradical, and

the radicals R, and R together with the shared C atom of the indoleninering can form a saturated S-membered or 6-membered ring,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5- membered or 6-membered ring whichoptionally possesses non-ionic substituents, or represents one or morecarboxy radicals,

R denotes hydrogen or a non-ionic substituent,

R denotes hydrogen or a non-ionic substituent and X represents ananion,' are manufactured if, in a manner which is in itself knownaromatic formyl compounds of the formula with9a-methyl-2,3,9,9a-tetrahydro-oxazolo- [3,2a1-indoles of the formula R,R3 (VIII N/ CH3 l l R4--CH- CH-R5 wherein R represents a lower alkylradical and R represents a lower alkyl radical, and

the radicals R and R together with the shared C atom of thedihydroindole ring can form a saturated S-membered or 6-membered ring,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5- mernbered or 6-membered ring whichoptionally possesses non-ionic substituents, or represents one or morecarboxy radicals,

R denotes hydrogen or a non-ionic substituent and R denotes hydrogen ora non-ionic substituent.

Suitable groups Ar according to' the invention are those groups of whichthe carbon atom located in the methine groups is a component of a cyclicplanar (4n+2)1relectron system which contains at least one donor groupin the 0- or p-position which is conjugated with the methine bridge.Aryl groups Ar are, according to the invention, carbocyclic groups Ar.

Possible donor groups are here above all the groupings OR, SR and Iwherein R represents an alkyl, aralkyl or aryl radical, R representshydrogen or an alkyl, aralkyl, alkenyl,

alkinyl or aryl radical and R" represents hydrogen or an alkyl, aralkylalkenyl, alkinyl or aryl radical, with the proviso that R and R" shallnot simultaneously denote hydrogen, and wherein these alkyl radicals canoptionally be cyclised via further hetero-atoms, such as O, S and NH,N-alkyl, N-aralkyl or N-ary], and wherein one of the radicals R and R"or both radicals can be linked to adjacent ring systems. Preferred donorgroups correspond to the formula radicals which are in the p-position tothe methine bridge are particularly preferred.

According to the invention, the Ar and Ar rings defined in more detailabove can also contain fused carbocyclic and heterocyclic rings.Possible groups Ar are, for example, optionally substituted,donor-substituted radicals of the benzene, naphthalene, benzofurane,benzothiophene, indole, indoline, 1,2,3 ,4- tetrahydroquinoline,carbazole, quinoxaline, dihydro-[benzo-l ,4-oxazine]-, dihydro-[ benzo-l,4- thiazine]-, 9,lO-dihydro-phenazine-, phenoxazineand phenthiazineseries. According to the invention, those groups of the benzene andnaphthalene series in which there is at least one amine-N- grouping inthe 0- or pposition to the methine group are preferred as groups Ar.

Suitable condensation components of the formula (VII) are, for example:

Table 3 p-(N-Dimethylamino)-benzaldehyde,p-(N-diethylamino)-benzaldehyde, p-(N-methyl-N-ethylamine)-benzaldehyde, p-(N-methyl-N-B-cyanoethylamino)-benzaldehyde,p-(N-methyl-N-B-chloroethylamino-benzaldehyde, 2-methyl-4-(N-ethyl-N-B-chloroethylamino)-benzaldehyde, 3-formyl-N- ethylcarbazole,3-formyl-N-methylcarbazole, 3-formyl- N-(n)-butylcarbazole, 4-formyl-N-methyldiphenylamine, 4-formyl-N-methyl-4- methyldiphenylamine,4-formyl-4'-methoxy-N- methyldiphenylamine, 4-formyl-4'-ethoxy-N-methyldiphenylamine, 4-formyl-4 '-chloro-N- methyldiphenylamine,4-formyl-2-chloro-N- methyldiphenylamine, 4-(N-piperidinyl)-benzaldehyde, p-( N-di-B-chloroethylamino)- benzaldehyde,p-'(N-ethyl-N-B-chloroethylamino)- benzaldehyde,p-(N-ethyl-N-B-cyanoethylamino benzaldehyde, p-(N-methyl-N-cyclohexyamino(sico) benzaldehyde,p-(N-di-n-propylamino)-benzaldehyde,p-(N-n-butyl-N-B-chloroethylamino)-benzaldehyde,p-[N-ethyl-N-(2-dimethylaminoethyl)amino]- benzaldehyde,p-(N-ethyl-N-benzylamino)- benzaldehyde,p-(N-ethyl-N-B-cyanoethylamino)- benzaldehyde,4-formyl-N-ethyldiphenylamine, 4-formyl-4'-methoxy-N-ethyldiphenylamine, 4-formyl-4-ethoxy-N-ethyldiphenylamine, 4-formyl-4'-methyl- N-ethyldiphenylamine,4-formyl-4'-chloro-N- ethyldiphenylamine, N-(p-formylphenyl)-morpholine,3-formyl-N-(n)-propylcarbazole, 6-formyl-l ,2,3 ,4-tetrahydro-9-ethylcarbazole.

Suitable oxazoloindoles of the formula (VIII) obtainable according tothe process of the invention are, for example:

Table 4 9,9,9a,-Trimethyl-2,3,9,9a-tetrahydro-oxazolo [3,2a]-indole,7,9,9,9a-tetramethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,7-chloro-9,9,9a-trimethyl- 2,3,9,9a tetrahydro-oxazolo-[3,2a]-indole,7-methoxy- 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,7-ethyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,7-cyclohexyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-trifluoromethyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,7-acetamino-9,9,9a-trimethyl- 2,3,9,Qa-tetrahydro-oxazolo-[3,2a]-indole,7- cyclohexyl- ,9a-tetramethyl-2,3,9,9a-tetrahydro-oxazolo-l3,221]-indole, 9,9-diethyl-9a-methyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,9,9-diethyl-7,9a-dimethyl- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,9,9-diethyl- 7-chloro-9a-methyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,2,9,9,9a-tetramethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole,3,9,9,9a-tetramethyl-2.3,9,9a-tctrahydro-oxazolo-[3,2a]-indole,9,9,9u-trimcthyl-2-phenoxy- 2.3,9,9a-tetrahydro-oxazolo-[3,2a1-indole,trimethyl- 2-phenoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,9,9,9a-trimethyl-7-methoxy-2-phenoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 9,9-diethyl-'9a-methyl-2-phenoxymethyl- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,trimethyl-Z- chloromethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,9,9,9a-trimethy1-3-chloromethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,9,9,9a-trimethyl-2- ethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,9,9,9-a-trimethyl-7phthalimidomethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,9,9,9a-trimethyl-7-cyano- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,2,9,9,9a-tetramethyl-7-cyano- 2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,2,3,9,9,9a-pentamethyl- 2,3,9,9a-tetrahydro-oxazolo-['3,2a]-indole,9,9,9atrimethyl-Z-methoxymethyl-Z,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,5,6-benzo-9,9,9a-trimethyl- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,6,7-benzo- 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[32a]- indole,6-chloro-9,9,9atrimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,5-chloro-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo- [3,2a]-indole,7-fluoro-9,9,9a-trimethyl-2,3,9,9atetrahydro-oxazolo-[3,2a1-indole,7-chloro-6-fluoro- 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a1-indole,7-benzyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,7-chloro-2-phenoxymethyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,7,9,9,9a-tetramethyl-2-phenoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-carboxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,7-(carbo-B-oxyethoxy)-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-carboxy-Z-phenoxymethyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-carboxy-3-phenoxymethyl-9,9,9a-trimethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]7-ethoxy-9,9,9a-trimethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]indole, 9,9,9a-trimethyl-2-ethoxymethyl-Z,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,9,9,9a-trimethyl-2-(n-propoxymethyl)-2,3,9,Qa-tetrahydro-oxazolo-[3,2a1-indole,9,9,9atrimethyl-2-(n-hexyloxymethyl)-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,9,9,9a-trimethyl-3- methoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 9,9,9a-trimethyl-3-ethoxymethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole,9,9,9a-trimethyl-3- (n-hexyloxymethyl)-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7,9,9,9a-tetramethyl-2-phenoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,9,9,9a-trimethyl-Z-phenoxymethyl-2,3,9,9a-

7-chloro- 10tetrahydro-oxazolo-[3,2a]-indole,7-fluoro-9,9,9atrimethyl-Z-phenoxymethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,7-chloro-9,9,9a-trimethyl-2- methoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3.2a]- indole, 7-chloro-9,9,9a-trimethyl-2-ethoxymethyl2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-chloro-9,9,9a-trimethyl-2-(n-hexyloxymethyl)-2,3,9,9atetrahydro-oxazolo-3,2a]aindole,7-chloro-9,9,9atrimethy1-2-(n-propoxymethyl)-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole,7-chloro-2,9,9,9a-tetramethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-chloro-3,9,9,9a-tetramethyl-2,3,9,9,a-tetrahydro-oxazolo- [3,2a]-indole,2,7,9,9,9a-pentamethyl-2,3,9,9,atetrahydro-oxazolo-[3,2a]-indole,3,7,9,9,9apentamethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole,7-chIoro-2,9,9,9a-tetramethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,7-chloro-3,9,9,9atetramethyl-2,3,9,9a-tetrahydro-oxazolo-[3,221]-indole,7-methylmercapto-9,9,9a-trimethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole,7-ethylmercapto- 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,7-methylsulphonyl-9,9,9a-trimethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole,9,9,9a-trimethyl-2- allyloxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole,9,9,9a-trimethyl-2-n-butoxymethyl-2,3,9,9atetrahydro-oxazolo-3,2a]-indole,9,9,9a-trimethyl-2-ndecyloxymethyl-2,3 ,9,9a-tetrahydro-oxazolo-[ 3,2a]- indole and 7,9,9,9a-tetramethyl-o-phthalimidomethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole.

The condensation can be carried out by stirring a solution of suspensionof equimolar amounts of the compounds (VII) and (VIII) in an organic orinorganic acid, or in a mixture thereof with water, l0l50C, preferablyat IOOC. Dilute aqueous mineral acids, such as sulphuric acid,phosphoric acid or hydrochloric acid, are for example suitable.

Particularly suitable organic acids are lower fatty acids, such asformic acid, acetic acid, propionic acid and butyric acid. Mixtures offormic acid, acetic acid, propionic acid or butyric acid with fatty acidanhydrides, such as acetic anhydride and propionic anhydride, are alsosuitable.

The condensation can also be carried out in a solvent, such as, say,benzene, toluene, chlorobenzene, methanol and ethanol, in the presenceof acid condensation agents, such as, say, formic acid, acetic acid,butyric acid, phosphorus pentoxide, zinc chloride, aluminium chloride,tin chloride, aqueous sulphuric acid,

- aqueous phosphoric acid or aqueous hydrochloric acid or theirmixtures,

Within the framework of the dyestuffs of the formula (VI), those areparticularly preferred, wherein R represents hydrogen, one or morenon-ionic substituents or the remaining part of a fused 5- membered or6-membered ring which optionally possesses non-ionic substituents,

especially those of the formula 1 l r 12 wherein R represents hydrogen,a lower alkyl radical, an aral- E represents a carbocyclic, aromaticradical which kyl radical or an aryl radi possesses a R representshydrogen, a lower alkyl radical, a lower alkenyl radical, a loweralkinyl radical or an aralkyl v radical,

R R represents hydrogen, a lower alkyl radical, a lower R" alkoxyradical, an aryl radical, fluorine, chlorine,

bromine, nitro, nitrile or the remaining part of a fused 6-membered ringwhich optionally possesses group in the p-position to the methinebridge, 10 nonionic substituents, and wherein X represents an anion.

R represents hydrogen or an alkyl, aralkyl, alkenyl, Within theframework of the dyestuffs of the formula alkinyl or aryl radical and(X), those are preferred R represents hydrogen or an alkyl, aralkyl,alkenyl, wherein alkinyl or aryl radical, with the proviso that R and Rrepresents hydroge One more "On-ionic R" do not simultaneously denotehydrogen, stituents or the remaining part of a fused 5- R, representsmethyl, ethyl or n-propyl, membered or 6-membered ring which optionallyR represents methyl, ethyl or n-propyl, possesses non-ionicsubstituents.

R represents hydrogen or one or more identical or Dyestuffs ofparticular importance are those of the different radicals from amongstmethyl, ethyl, fluofOrmUla rine, chlorine, trifluoromethyl, n-propyl,tert.- butyl, n-hexyl, n-dodecyl, cyclohexyl, phenyl, 4- nitrophenyl,4-methoxyphenyl, benzyl, methoxy,

ethoxy, n-propoxy, n-butoxy, methylmercapto, ethylmercapto,methylsulphonyl, acetamino, phenoxy, carbomethoxy, carboethoxy,carbophenoxy, R v sulphamoyl or nitrile, and R and R indepen- 3 N dentlyof one another represent hydrogen, methyl, I (Xi ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-nonyl, chloromethyl, methoxymethyl,ethoxymethyl, npropoxymethyl, n-butoxymethyl, n-hexoxymethyl,n-octyloxymethyl, n-nonyloxymethyl, ndodecyloxymethyl, phenoxymethyl,phenyl, 4-

chlorophenyl, 4-nitrophenyl, 4-methoxyphenyl, carbomethoxy, carboethoxy,carbophenoxy or niwherein trile and R represents methyl, ethyl orn-propyl, X represents an anion. R represents methyl, ethyl or n-propyl,A further Outstanding group of rnethine dyestuffs ac- R representshydrogen, one or more identical or difcording to the inventioncorresponds to the general forferent radicals from amongst methyl,ethyl, nmula propyl, fluorine, chlorine, trifluoromethyl, tert.-

butyl, n-hexyl, n-dodecyl, cyclohexyl, phenyl, 4- nitrophenyl,4-methoxyphenyl, benzyl, methoxy, ethoxy, n-propoxy, n-butoxy,methylmercapto,

ethylmercapto, methylsulphonyl, acetamino, phe- R noxy, carboethoxy,sulphamoyl or nitrile, and

R R and R independently of one another represent j[' 2 TL hydrogen,methyl, ethyl, n-propyl, n-butyl, n- 4-03431- *8 pentyl, n-hexyl,n-nonyl, chloromethyl, methox- R ymethyl, ethoxymethyl, n-propoxymethyl,n- E 4 butoxymethyl, n-hexyloxymethyl, n- CR HOH octyloxymethyl,n-nonyloxymethyl, n- 5 dodecyloxymethyl, phenoxymethyl, phenyl, 4-

chlorophenyl, 4-nitrophenyl, 4-methoxyphenyl, carbomethoxy, carboethoxy,carbophenoxy, al-

wherein p lyloxymethyl, chlorine or nitrile,

R represents a lower alkyl radical and R represents hydrogen, methyl,ethyl, n-propyl, 4 R represents a lower alkyl radical, and the radicalschlorophenyl, 4-methoxyphenyl or benzyl,

R and R together with the shared (bond) of the R represents hydrogen,methyl, ethyl, n-propyl, isoindolenine ring can form a saturatedS-membered propyl, n-butyl, iso-butyl or benzyl, or 6-membered ring, Rrepresents hydrogen, methyl, ethyl, chlorine, R represents hydrogen, oneor more non-ionic subphenyl or the remaining part of a fused partly orstituents or the remaining part of a fused S-member wholly unsaturatedcarbocyclic 6-membered ring or 6-membered ring which optionallypossesses and non-ionic substituents, or represents one or more 6 Xrepresents an anion. carboxy radical Dyestuffs of the formula (X) areobtainable in a sur- R represents hydrogen or a non-ionic substituentprising manner if, in a manner which is in itself known,

R represents hydrogen or a non-ionic substituent ind9l-3-aldehydes ofthe formula O=C W9 (XI) wherein R R and R have the abovementionedmeaning, or functionally similar compounds, are condensed with9amethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]- indoles of the formula (1).

Such functionally similar compounds are, especially, primary products ofthe Vilsmeier reaction, Schiffs bases, azomethines, oximes, nitrones andhydrazones.

The condensation can be carried out by stirring a solution or suspensionof equimolar amounts of the compounds (I) and (XI), or functionallysimilar compounds, in an organic or inorganic acid or its mixture withwater. Temperatures of about 10 to about 150C, preferably of 40 to 100C,are chosen as the reaction temperature. Dilute aqueous mineral acids,such as sulphuric acid, phosphoric acid or hydrochloric acid, are forexample suitable. Lower fatty acids, such as formic acid, acetic acid,propionic acid and butyric acid, and their mixtures with fatty acidanhydrides, such as acetic anhydride and propionic anhydride, areparticularly suitable. The condensation can also be carried out in thepresence of an organic solvent, such as benzene, toluene, chlorobenzene,acetonitrile, methanol or etha-v nol.

Suitable 9a-methyl-2,3,9,9a-tetrahydrooxazolo- [3,2a]-indoles are, forexample, those listed in Table 4. Suitable indol-3-aldehydes are, forexample, those listed in the following Table 2-Phenylindol-3-aldehyde,l-methyl-Z-phenylindol- 3-aldehyde, l-methyl-5-methoxy-2-phenylindol-3-aldehyde, l-methyl-5-chloroindol-3-aldehyde, 1,5-dimethyl-2-phenylindol-3-aldehyde, 2-methyl-7- ethylindol-3-aldehyde,5-nitro-2-methyl-7-ethylindol- 3-aldehyde,l-ethyl-2-methyl-6,7-benzoindol-3- aldehyde,l-ethyl-2-phenylindol-3-aldehyde and 2-(4-chlorophenyl)-7-ethylindol-3-aldehyde.

Dyestuffs of the formula (X), wherein R represents hydrogen, one or morenon-ionic substituents or the remaining part of a fused 5- membered or6-membered ring which optionally possesses non-ionic substituents, orrepresents one or more carboxy radicals, and those of the formula (Xa),can be prepared in the same manner.

A further preferred group of methine dyestuffs according to theinvention corresponds to the formula wherein R represents a lower alkylradical and R represents a lower alkyl radical, and the radicals R and Rtogether with the shared C atom of the indolenine ring can form asaturated S-membered or 6-membered ring,

R represents a lower alkyl radical,

R represents a lower alkyl radical,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5- membered or 6-membered ring or representscarboxyl,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5 membered or 6-membered ring or representscarboxyl,

R denotes hydrogen or a non-ionic substituent,

R denotes hydrogen or a non-ionic substituent,

R denotes a lower alkyl or aralkyl radical and X" denotes an anion.

Dyestuffs of particular importance are those of the formula ymethyl,ethoxymethyl, n-propoxymethyl, nbutoxymethyl, n-hexyloxymethyl,noctyloxymethyl, n-nonyloxymethyl, n-

dodecyloxymethyl, phenoxymethyl, phenyl, 4- nitrophenyl, 4-chlorophenyl,4-methoxyphenyl, carbomethoxy, carboethoxy, carbophenoxy,allyloxymethyl, chlorine or nitrile,

R represents methyl, ethyl, n-propyl or benzyl and X represents ananion.

Dyestuffs of the formula XII are manufactured if aldehydes of theformula (XIIa) Table 6 1,3 ,3 -Trimethyl-2-formylmethyleneindoline,trimethyl-S -chloro-2-formylmethyleneindoline, trimethyl-S-nitro-2-formylmethyleneindoline,trimethyl-S-methoxy-2-forrnylmethyleneindoline, 1,3,-3-trimethyl-5-carbomethoxy-2-formylmethyleneindoline, 1,3,3-trimethyl--carboethoxy-2-formylmethyleneindoline,l,3,3,5-tetramethyl-2 formylmethyleneindoline, 1,3,3-trimethyl-5-cyano-2-formylmethyleneindoline, 1,3,3-trimethyl-5-ethyl-2-formylmethyleneindoline,l,3,3-trimethyl-5-benzyl-2-formylmethyleneindoline,l-methyl-3,3-diethyl-2-formylmethyleneindoline, l-methyl-3 ,3-diethyl-5-chloro-2- formylmethyleneindoline, 1-methyl-3,3-diethyl-5-methoxy-Z-formylmethyleneindoline, 1,3,3-trimethyl-6,7-benzo-2-formylmethyleneindoline, 1-ethyl-3 ,3-dimethyl-2-formylmethyleneindoline, 1,3,3-triethyl-2-formylmethyleneindoline, 1,3,3-trimethyl-5-acetamino-Z-formylmethyleneindoline and 1,3,3-trimethyl-S-sulphamoyl-2-formylmethyleneindoline.

Particularly preferred dyestuffs are those of the formulae (V1) to(XI1), wherein R and R or R and R represent hydrogen, or wherein one ofthe radicals R; and R or R and R represents hydrogen and the otherrepresents a methyl radical, a chloromethyl radical, a phenyl radical, aphenoxymethyl radical, a methoxymethyl radical, an allyloxymethylradical or a nhexoxymethyl radical. From an economic point of view,particularly interesting dyestuffs are those of the formulae (V11) to(X11), wherein R and R or R and R represent hydrogen or one of theradicals R and R or R and R represents methyl.

Compounds of the formulae (V1) and (IX). wherein R and R or R and Rrepresent hydrogen, are of outstanding importance.

The groups of dyestuffs singled out here as being particularlyinteresting and suitable are also obtainable according to the process ofthe invention.

Hydrazone dyestuffs according to the invention, of the formula Rrepresents a lower alkyl radical and R represents a lower alkyl radical,and

the radicals R, and R together with the shared C atom of the indoleninering can form a saturated S-membered or 6-membered ring,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5- membered or 6-membered ring whichoptionally possesses non-ionic substituents, or represents one or morecarboxy radicals,

R represents hydrogen or a non-ionic substituent,

R represents hydrogen or a non-ionic substituent,

R denotes an alkyl, alkenyl or aralkyl radical and X' represents ananion, can be manufactured if azo bases of the formula N CH-N N-Aryl(Xv) E 4 (moan H N aryl (XVI) are diazotised and coupled with compoundsof the formula 1 a CH- cm R5 ,wherein R represents a lower alkyl radicaland R represents a lower alkyl radical, and

the radicals R and R together with the shared C atom of thedihydroindole ring can form a saturated S-membered or 6-membered ring,

R represents hydrogen, one or more non-ionic substituents or theremaining part of a fused 5- membered or 6-membered ring whichoptionally possesses non-ionic substituents, or represents one or morecarboxyl radicals,

R denotes hydrogen or a non-ionic substituent and R denotes hydrogen ora nonionic substituent, and

the coupling product obtained is treated with acidbinding substances,such as, for example, alkali, in a manner which is in itself known.

1f mixtures of compounds of the formula V111 are used, mixtures of azobases are produced.

The alkylation can be carried out by warming the solution or suspensionof a compound of the formula (XV) in an inert medium with the alkylatingagent to 60l50C, preferably 80-l20C. For this purpose, it is alsopossible to use an excess of the alkylating agent as the solvent.

Suitable insert media are, for example, organic liquids, such asbenzine, ligroin, cyclohexane, benzene, toluene, chloroform,c'hlorobenzene and dichlorobenzene, nitrobenzene, tetralin, dioxane anddimethylformamide.

Suitable alkylating agents are, for example, dimethyl sulphate, diethylsulphate and di-n-butyl sulphate; benzenesulphonic acid methyl, ethyl,n-propyl, iso-propyl and iso-butyl esters; toluenesulphonic acid methyl,ethyl, n-propyl, isopropyl and iso-butyl esters; methyl iodide, ethyliodide, n-butyl bromide, allyl chloride, allyl bromide, Z-chloroand2-bromo-diethyl ether, and also chloroand bromo-acetic acid esters, suchas chloroand bromo-acetic acid ethyl ester. Dimethyl sulphate isparticularly suitable.

The alkylation can also be carried out in the presence of alkalineagents, especially in the presence of tertiary amines which aresubstituted at the N-atom, in accordance with Belgian PatentSpecification No. 735,565. A particularly suitable amine with bulkysubstituents is triisopropanolamine Preferred dyestuffs of the formula(XIV) are those, wherein R represents hydrogen, one or more non-ionicsubstituents or the remaining part of a fused membered or 6-memberedring which optionally possesses non-ionic substitutents.

Particularly preferred dyestuffs of the formula (XIV) are those whereinR and R represent hydrogen mom of the radicals R and R representshydrogen and the other represents a methyl radical, a methoxymethylradical, a n-hexoxymethyl radical, a chloromethyl radical, a phenylradical, an allyloxymethyl radical or a phenoxymethyl radical.

Dyestuffs of the formula (XIV), wherein R, and R represent hydrogen orone of the radicals R. and R5 rerzrq gnls M99592 adl p M1 2 represents amethyl radical A N are of outstanding importance. From an economic pointof view, dyestuffs of the formula (XIV), wherein R and R representhydrogen are of particular inter- ESL As examples of suitable aminecomponents of the formula (XVI) there may be mentioned: aniline,ptoluidine, m-toluidine, p-anisidine, m-anisidine, oanisidine,p-phenetidine, o-phenetidine, 4-aminoacetanilide,N-benzoyl-p-phenylenediamine, 5-amino- 2-acetylaminoanisole,4-amino-2,5-diethoxybenzoic acid anilide,4-amino-2methyl-5-methoxybenzanilide, l-amino-4-ethylbenzene,l-amino-4-tert.- butylbenzene, 2,4,5-trimethylaniline, 2,3,5-trimethylaniline, 6-amino-3-methoxytoluene, l-amino-3-chloro-4-methoxybenzene, l-amino-2,4- dimethoxybenzene,l-amino-2,S-dimethoxy-benzene, l-amino-2,4-diethoxybenzene, I-amino-3,4-

dimethoxybenzene, l-amino-3,4-diethoxybenzene, 2- chloro-4-aminoanisole,3 ,4-dicyanoaniline, 4-

aminoazobenzene, 4-aminoazotoluene, dehydrothiotoluidine,4-chloroaniline, 4-fluoroaniline, 2-

chloroaniline, 3-chloroaniline, 2,4-dichloroaniline, 2,4-dimethoxy-S-chloroaniline, 4-aminodiphenylmethane,4-aminodiphenylethane-( 1,2), 4-amino-4'- nitrodiphenylmethane,4,4-diaminodiphenylmethane, 4-amino-4-methyldiphenylmethane, 4.-amino-4-hydroxydiphenylmethane, 4-amino-4'- methoxydiphenylmethane, 1,2,3,4-tetrahydro-5- aminonaphthalene, 4-cyclohexylaniline, 2-methyl-4-cyclohexylaniline, l-aminonaphthalene, 3-amino-N- ethylcarbazole,4-amino-4-ethoxy-N- methyldiphenylamine, 4-amino-diphenylene oxide, 3-amino-diphenylene oxide, 3-aminodiphenylene sulphide,4-aminodiphenyl-ether, 4-amino4- methyldiphenyl-ether,4-aminophenylbenzyl-ether, 4- aminophenyl-a-naphthyl-ether,4-aminodiphenyl sulphide, 4-amino-4'-methoxydiphenyl-ether,3-aminophenylbenzyl-ether and 4-aminophenyl-pchlorobenzyl-ether.

When using oxazolindole mixtures for the manufacture of basic dyestuffsof the formulae VI, IX, X, Xa, XII, XIII and XIV, dyestuff mixtures areproduced.

A replacement of dyestuff anions by other dyestuff anions can be carriedout according to known processes. For example, the basic dyestuffs canbe treated with acid-binding agents, such as sodium carbonate, potassiumcarbonate, ammonium carbonate, magnesium carbonate, sodium hydroxide,potassium hydroxide, ammonia and silver oxide, optionally in an aqueousmedium, whereupon the dyestuff-onium base or the carbinol base. areproduced, and these can be treated with anion-donating agents, theseanions being different from those of the basic dyestuff employed.

The new products (II),-(VI), (IX), (X), (Xa), (XII), (XIII) and (XIV)are valuable dyestuffs which can be used for dyeing and printingmaterials of leather, tannin-treated cotton, cellulose, syntheticpolyamides and polyurethanes and for dyeing lignin-containing fibres,such as coir, jute and sisal. They are furthermore suitable for themanufacture of writing fluids, rubberstamp inks, and ball pen pastes andcan also be used in flexographic printing.

Suitable materials for dyeing with the basic dyestuffs of the abovegeneral formulae (II), (VI), (X), (Xa), (XII), (XIII) and (XIV) are, inparticular, flocks, fibres, filaments, tapes, woven fabrics or knittedfabrics of polyacrylonitrile or of copolymers of acrylonitrile withother vinyl compounds, such as vinyl chloride, vinylidene chloride,vinyl fluoride, vinyl acetate, vinylpyridine, vinylimidazole, vinylalcohol, acrylic and methacrylic acid esters and amides and asymmetricaldicyanoethylene, or flocks, fibres, filaments, tapes, woven fabrics orknitted fabrics of acid-modified aromatic polyester fibres andacid-modified polyamide fibres.

Acid-modified aromatic polyesters are, for example, polycondensationproducts of sulphoterephthalic acid and ethylene glycol, that is to saypolyethylene glycol terephthalates containing sulphonic acid groups(type DACRON 64 of El. DuPont de Nemours and Company), such as aredescribed in Belgian Patent Specification No. 549,170 and in US. Pat.No. 2,893,816.

Dyeing can be effected from a weakly acid liquor, with the goodsappropriately being introduced into the dyebath at 40- 60C and then dyedat the boil. It is also possible to dye under pressure at temperaturesabove 100C. Furthermore, the dyestuffs can be added to spinningsolutions for the manufacture of fibres containing polyacrylonitrile orcan be applied to the unstretched fibre.

The dyeings of the dyestuffs according to the invention, of the formulae(ll), (IV), (IX) (X), (Xa), (XII), (XIII) and (XlV), on materials ofpolyacrylonitrile or acid-modified polyester fibres are distinguished byvery good fastness to light, wet processing, rubbing and sublimation.

With anionic prccipitants such as alumina, tannin, phosphotungstic acidand phosphomolybdic acid the dyestuffs form light-fast pigments whichcan advantageously be employed in paper printing.

The dyestuffs can be used individually or as mixtures. They are verysuitable for dyeing shaped articles of polymers or copolymers ofacrylonitrile, asymmetrical dicyanoethylene, acid-modified aromaticpolyesters or acid-modified synthetic polyarnides in chlorinatedhydrocarbons as the dyebath, provided they possess substituents, suchas, for example, the tert.-butyl group, which assist the solubility inchlorinated hydrocarbons, or provided the anion X is the anion of amonobasic, organic acid with 4-30 carbon atoms.

Examples of such organic acids are: 2- ethylenecaproic acid, lauricacid, oleic acid, linoleic acid, a mixture of aliphatic carboxylic acidswith -19 carbon atoms (Versatic Acid 1519), a mixture of aliphaticcarboxylic acids with 9ll carbon atoms (Versatic Acid 91 l coconut fattyacid first runnings, tetradecanoic acid, undecylenoic acid,dimethylpropanoic acid, dimethylacetic acid, carboxylic acids of whichthe carbon chain is interrupted by heteroatoms, such asnonylphenol-tetraethylene-glycol-etherpropionic acid,nonylphenoldiethylene-glycol-etherpropionic acid,dodecyltetraethylene-glycol-etherpripionic acid, 3-(nonyloxy)-propionicacid, 3-(isotridecyloxy)-propionic acid, 3-(isotridecyloxy)-diethylene-glycol-ether-propionic acid, 3-(isotridecyloxy)-diethylene-glycol-ether-propionic acid, ether-propionicacid of the alcohol mixture with 6-10 carbon atoms, nonylphenoxyaceticacid, aromatic carboxylic acids, such as tert.-butyl-benzoic acid,cycloaliphatic carboxylic'acids, such as hexahydrobenzoic acid,cyclohexencarboxylic acid and abietic acid, and sulphonic acid, such astetrapropylenebenzenesulphonic acid.

Dyestuffs in which the anion A is the anion of one of the acids listedhere are particularly preferred.

If the dyestuffs according to the invention are in the form of salts ofthe monobasic organic acids with b 4-30 carbon atoms which have beenmentioned, concentrated solutions of good stability of three dyestuffsin chlorinated hydrocarbons can be manufactured, if appropriate with theaddition of polar organic solvents which are completely miscible withchlorinated hydrocarbons, such as butyrolactone, dimethylformamide,methanol, dioxane, acetonitrile, methyl ethyl ketone, nitrobenzene,dimethylsulphoxide, benzonitrile and 2- nitrochlorobenzene.

To manufacture such solutions, the dyestuffs according to the invention,in the form of the free bases or carbinol bases, or as salts of organicacids with 4-30 carbon atoms, are stirred with chlorinated hydrocarbonsand monobasic organic acids with 4-30 carbon atoms, if appropriate withthe addition of polar organic solvents which are completely misciblewith chlorinated EXAMPLE 1 Ethylene oxide is passed into a mixture of gof 2,3,3-trimethylindolenine and 400 g of glacial acetic acid at 4045Cfor 3 /2 hours. The reaction mixture is then introduced into 2,000 ml ofice/water and rendered alkaline with concentrated sodium hydroxidesolution. The oil which has separated out is taken up in 300 ml ofligroin. The ligroin phase is dried with Na 80,, the ligroin isevaporated off and the residue is distilled to yield 74 g of a liquidwhich passes over at 78 80C and 0.1 mm Hg, of the formula N CH C CH

which crystallises to give a colourless substance of melting point: 4446.

Analysis: C H N 0 calculated: 76.8 8.4 6.9 7.9 found: 76.1 8.6 6.9 8.2

EXAMPLE 2 If ethylene oxide is passed into a mixture of 80 g of2,3,B-trimethylindolenine and 300 g of glacial acetic acid at 6065C for6 hours, working up analogously to Example 1 yields 76.7 g of thereaction product, passing over at 92C and 0.3 mm Hg, the constitution ofwhich has been indicated in Example 1.

EXAMPLE 3 If ethylene oxide is passed into a mixture of 80 g of2,3,3-trimethylinolenine, 90 g of glacial acetic acid and 210 g of waterat 45C for 6 hours, working up analogously to Example 1 yields 78.6 g ofthe reaction produt which passes over a 87C and 0.2 mm Hg and has theconstitution indicated in Example 1.

EXAMPLE 3 If ethylene oxide is passed into a mixture of 80 g of2,3,3-trimethylindolenine, 90 g of glacial acetic acid and 210 g ofwater at 45C for 6 hours, working up analogously to Example 1 yields78.6 g of the reaction product which passes over at 87C and 0.2 mm Hgand has the constitution indicated in Example 1.

EXAMPLE 4 60 g of propylene oxide are added dropwise over the course of3 hours to a mixture of 45 g of 2,3,3- trimethylindolenine and 300 g ofglacial acetic acid at 50C, whilst stirring. The reaction mixture isstirred for a further 2 hours at 50C and is introduced into approx.3,000 ml of ice/water, the whole is rendered alkaline with concentratedsodium hydroxide solution and the oil which has separated out is takenup in twice 300 ml of ligroin. After drying with Na SO and evaporatingoff the ligroin, a residue remains from which, after fractionaldistillation, 13.8 g of the reaction product, passing over as a lightyellow oil at 95-100C and 0.3 mm Hg, are obtained. The productcorresponds to an approximate composition of:

50 g of epichlorohydrin are added dropwise over the course of 4 hours toa mixture of 80 g of 2,3,3- trimethylindolenine and 300 g of glacialacetic acid at 60C, whilst stirring, and the mixture is then stirred fora further 2 hours at 80C. It is then poured into 2,000 g of ice/waterand carefully rendered alkaline with sodium hydroxide solution, whilstkeeping the mixture at ml of benzene. The residue which remains onevaporating off the benzene phase after fractional distillation yields10.6 g of the reaction product which passes over at 155160C and 0.2 mmHg.

Composition: mixture of and 0 Q I I i 4111 CH2 CH2 on EXAMPLE 7 80 g ofphenoxypropylene oxide are added dropwise over the course of2 hours to amixture of 80 g of 2,3,3- trimethylindolenine and 300 g of glacialacetic acid at 80C, whilst stirring, and the mixture is subsequentlystirred for a further 2 hours at 80C. The reaction mix ture isintroduced into 1,500 g of ice/water and rendered alkaline withconcentrated sodium hydroxide solution, and the oil which has separatedout is taken up in 400 ml of benzene. The benzene phase is dried with NaSQ, and thereafter, following evaporation of the benzene, the residue isdistilled under reduced pressure. 33.7 g of the reaction product, whichpasses over at 150162C and 0.1 mm Hg and solidifes on cooling, areobtained: Melting point: 64-68C.

Composition: mixture of CH CH CH CH O N O -O-CH -CH-CH 0C, and the oilwhich separates out is taken up in twice 200 ml of ligroin. Afterevaporating off the ligroin, an oil remains, from which 31.5 g of theliquid reaction product, passing over at l 16-l25C and 0.3 mm Hg, areobtained after fractional distillation. Composition: mixture of 70 g ofstyrene oxide are added dropwise over the course of 1% hours to amixture of 80 g of 2,3,3- trimethylindolenine and 300 g of glacialacetic acid at 80C and the mixture is then stirred for a further hour at80C. The reaction mixture is introduced into 1,500 ml of ice/water, thenrendered alkaline with concentrated sodium hydroxide solution andtreated with 400 Analysis: C H N calculated: 7608 7 7 4.7 10.8 found:77.8 7.9 4.6 10.9

EXAMPLE 8 20 g of 5-cyclohexyl-2,3,3,7-tetramethylindolenine in g ofglacial acetic acid are reacted with ethylene oxide for 2 /2 hours at35C. The reaction mixture is worked up analogously to Example 7.Hereupon, 10.2 g of the reaction product which passes over at 130C and0.1 mm Hg and is viscous at room temperature, of the constitution l l CHCH CH are obtained.

EXAMPLE 9 Ethylene oxide is passed into a mixture of 60 g of 5-methoxy-2,3,3-trimethylindolenine and 300 g of glacial acetic acid at40C for 5 hours, whilst stirring. Working up takes place analogously toExample 7. Hereupon, 29.5 g of the reaction product are obtained as anoil which passes over at l04-108C and 0.1 mm Hg and is viscous at roomtemperature.

Constitution:

H CO CH3 3 cm 1 CH o v I CH CH Analysis: C H N calculated: 72.1 8.2 6.013.7 found: 71.8 8.5 6.2 13.8

EXAMPLE l0 Ethylene oxide is passed through a solution of 20 g of5-(phthalimidomethylene)-2,3,3- trimethylindolenine in 250 g of glacialacetic acid at 40C for 5 hours. The reaction mixture is then introducedinto 1,500 ml of ice/water and carefully rendered alkaline with sodiumhydroxide solution whilst maintaining a temperature of approx. 0C. Thesolid product which precipitates is washed with water until neutral andthen recrystallised from dimethylformamide.

Yield: 8.5 g; Melting point: 197-l98C.

16 g of phenoxypropylene oxide are added dropwise over the course of 1hour to a solution of 20 g of- 2,3,3-trimethylindolenine- S-carboxylicacid in 100 g of glacial acetic acid at 60C, whilst stirring. Thereaction mixture is stirred for a further hour at 80C, introduced into600 g of ice/water and rendered alkaline with 20% strength sodiumhydroxide solution, whereupon the product dissolves apart from a smallproportion of oil. The solution is treated with charcoal and filtered,and the filtrate is adjusted to pH 5-6 whilst keeping the temperature at0C. Hereupon the reaction product precipitates as a lumpy mass. This isthen again stirred with 250 ml of 5% strength sodium hydroxide solutionfor 3 hours at 60C; after treatment with charcoal, the filtrate isadjusted to pH 56 with concentrated hydrochloric acid whilst cooling to0C. The mass which procipitates in a flocculent form and is almostcolourless is recrystallised from methanol/water (5 1).

Melting point: 181 183C.

Constitution: mixture of and 0H H00 I c1-1 v I CH -CH-CH -O- Analysis: CH N 0 calculated: 71.4 6.5 4.0 18.1 found: 70.5 6.7 4.0 18.2

EXAMPLE 12 40 g of 1-(n)-hexyloxy-2,3-epoxypropane are added dropwiseover the course of 2 hours to a solution of 40 g of2,3,3-trimethylindolenine in 250 ml of glacial acetic acid at C. Themixture is stirred for a further hour at 120, a further 10 g ofl-(n)-hexyloxy-2,3- epoxypropane are added dropwise at 120, and thewhole is again stirred for a further 2 hours at 120. The reactionmixture is then introduced into 1,500 ml of ice/water and renderedalkaline with sodium hydroxide solution at 0C, and the oil whichseparates out is taken up in benzene. After drying the benzene phasewith Na SO and distilling off the benzene, an oil remains.

which is fractionated at 0.1 mm Hg. Hereupon, the reaction productpasses over at -145 and 0.1 mm Hg, as a mixture of the two components:

I CH2- cm-ca --o--(ca -cm and calculated: found: 7

EXAMPLE 13 sulphate for 6 hours at 80C. The chlorobenzene is then 60 gof glycidallyl-ether are added dropwise over the removed by Steam dit11la tin and the cnfdefl'oduct course of 2 hours t a i t of 80 g f 233.which precipitates 1S purified by recrystallisation fromtrimethylindolenine and 300 ml of glacial acetic acid at Water with theaddition of charcoal- The dyestuff of the 80C, the mixture is stirredfor a further hour at 80C, 5 formula OH II N- Q 0 CH (H1 80 c'm -cu on 3a further 20 g of glycidallyl-ether are added dropwise which is obtainedin yellow crystals dyes materials of over the course of 1 hour at 100C,and the whole is polyacrylonitrile in reddish-tinged yellow shades ofstirred for a further hour at 100C. The reaction mixgood fastness tolight and to wet processing.

ture is then introduced into 2 kg of ice water and is rendered alkalinewith sodium hyroxide solution, and the EXAMPLE 15 oil which hasseparated out is taken up in ligroin and g of 3- min -N- hy arediaZOtiSed, in fractionated after evaporating off the solvent. 69.4 g ofa ixture Of 200 ml of Water and 16 ml of strength a colourless oil,which passes over at 155C and 1.5 mm aqueous hy rochloric acid, wi h 30%s rength aqueous Hg, is obtained as a mixture of the following twocomsodium nitrite solution-at 10C. The diazonium solution ponents:obtained after destroying excess nitrite and after filtra- CH ca r---i--CH H approx. 67% and approx. 33% ll 3 I 3 CH CH-CH -OCH CH CH CH =CHCHO'-CH Cll-Cli Analysis: C H N 0 tion is treated dropwise over the courseof 1 hour, at

gs gf 33-3 2? approx. 10C, with 11.7 g of the product obtained ac- 35cording to Example 9. The mixture is then neutralised to pH 5.over thecourse of 5 hours by means of 20% EXAMPLE 14 strength aqueous sodiumacetate solution, the tempera- 9.2 g of p-anisidine are dissolved in amixture of 24 ture rising to approx. 20C towards the end. The azo ml of30% strength aqueous hydrochloric acid and 300 base liberated by addingalkali is filtered off, washed ml of water and diazotised with 30%strength aqueous 40 with water until neutral and dried in vacuo at 60C.sodium nitrite solution at 0C. After destroying excess Yield: 20.7 g;Melting point: 127-130C (benzene/linitrite by adding amidosulphonicacid, 15.3 g of the groin).

substance obtained according to Example 1 are added For the alkylation,12 g of the azo base in 100 ml of dropwise over the course of 1% hoursat 05C. The anhydrous chlorobenzene are treated with 1.0 g of trimixtureis then neutralised to pH 5 over the course of isopropanolamine and thenreacted with 4.8 g of di- 4 hours by means of 20% strength sodiumacetate solumethyl sulphate at 80-85C for 6 hours. The residue tion, thetemperature rising to 15C towards the end. which remains after removingthe chlorobenzene is re- The pH is then adjusted to 9 with 10% strengthsodium crystallised from water after addition of charcoal. The hydroxidesolution and the mixture is stirred for 15 dyestuff of the formula n,/ Ha] q CH3SO4 CH I CH -CH OH 3 0 3 hours at room temperature.The productwhich precipiis obtained as red-violet crystals and dyes fabrics oftates is filtered off, washed with water until neutral,polyacrylonitrile in red-violet shades of good fastness dried in vacuoat C and recrystallised from methato light and to wet processing. nolwith the addition of charcoal. Red crystals of melt- If the startingcomponents listed in the table which ing point: 129 130C; Yield: 17.6 g.follows are used for the manufacture of the azo bases, For thealkylation, 15.2 g of azo base in ml of analkylation with dimethylsulphate yields dyestuffs hydrous chlorobenzene are treated with 1.0 gof triisowhich dye fabrics of polyacrylonitrile in the colourpropanolamine and then reacted with 8.7 gof dimethyl shades indicated.

Amine Component Coupling Component Colour shade p-anisidine4-benzylaniline l-amino-3 .4-dimethoxybenzene l-amino-4-chlorobenzene4-aminobenzophenone 3-amino-4-methylbenzophenone 4-aminodiphenyl-ether4-aminoazobenzene 3-amino-N-elhylcarbazole 4-cyclohexylanilinea-naphthylamine Z-aminodiphenyl oxide phenyl-( 4-aminobenzyl )-sulphonetelrahydro-u-naphthylamine p-anisidine 4-aminodiphenylmethane anilinep-anisidine p-anisidine 3-amino-N-ethylcarbazole a-naphthylaminetetrahydro-a-naphthylamine 4-aminodiphenyl sulphide 4amino4'-methoxydiphenylmethane 4-amino-4'-nitrodiphenylmethane p-toluidinep-anisidine 3-amino-N-ethylcarbazole p-toluidine p-anisidinep-phenetidine aniline p-toluidine aniline 4-aminodiphenylmethanep-toluidine 4-aminodiphenylmethane p-toluidine 4-aminodiphenylmethanep-anisidine 4amino-4-methyldiphenylmethane 3-amino-N -ethylcarbazolep-anisidine p-toluidine 3-amino-N-methylcarbazole 3-aminobenzophenonepanisidine 4-amino4'nitrodiphenylmethane I4-amino-4-nitrodiphenylmethane p-anisidine p-toluidine according toExample 1 according to Example 1 do. do. do. do. do. do. according toExample 107-chloro9,9,9a-trimethyl-2,3,9,9atetrahydrooxazolo-l3,2al-indole o.7-chloro-9,9,9a-trimethyl 2.3,9,9atetrahydrdooxazolo-l3.2al-indole do.do. do. do. according to Example 13 do.

do. 7-methyl9,9,9a-trin1ethyl-2,3,9,9atetrahydrooxazolo-l3,2al-indole7-trifluoromethyl-9,9.9a-trimethyl- 2,3 ,9,9a-tetrahydrooxazolo-[3,2a]-indole do. according to Example 1 according to Example 5 accordingto Example 9 do. do. according to Example 7 do.

according to Example 12 do. do.

according to Example 8 7-cyclohexyl-9,9 ,9a-trimethyl-2,3,9,

9a-tetrahydrooxazolo-[3 ,ZaI-indole do.

7-cyclohexyl-9,9,9a-trimethyl-2,3 ,9, 9a-tetrahydrooxazolo-[ 3 .28l-indole 7-fluoro-9,9,9a-trimethyl-2,3 9.9atetrahydrooxazolo-l 3.2al-indole dov do.

do. 5 chloro-9,9,9a-trimethyl-2,3,9.9atetrahydrooxazolo 3,2a]-indole do.

according to Example 6 do. according to Example 1 1 yellow yellowreddish tinged yellow orange orange orange yellow yellow yellowreddish-tinged yellow reddish-tinged yellow yellow reddish-tinged yellowyellow reddish-tinged yellow reddishtinged yellow reddish-tinged yelloworange reddish-tinged yellow orange red red

yellow reddish-tinged yellow yellow yellow reddishdinged yellowreddish-tinged yellow orange yellow reddish-tinged yellow yellowreddish-tinged yellow orange red yellow reddish-tinged yellowreddish-tinged yellow reddish-tinged yellow yellow reddish-tinged yellowreddish-tinged yellow yellow reddish-tinged yellow reddish-tinged yellowred reddish-tinged yellow yellow yellow reddish-tinged yellowreddish-tinged yellow reddish-tinged yellow orange bluish-tinged redyellow reddish'tinged yellow reddish-tinged yellow yellow yellow yellowyellow yellow yellow yellow reddish-tinged yellow reddish-tinged yellowreddish-tinged yellow red reddish-tinged yellow yellow red yellowreddish-tinged yellow reddish-tinged yellow reddish-tinged yellowreddish-tinged yellow reddish-tinged yellow EXAMPLE 16 25 ml ofglacialacetic acid and 3 ml ot'acetic anhydride 4 g f the reaction productobtained in Example 1 are stirred for 6 hours at 90-l()OC. The reactionmixand 5 g f 4 f ]-4 th N- th ]di h l i ture 18 then ntroduced into 109ml of 1Q strength in a mi ture f 35 g f l i l acetic id d 2 g f aqueoussodium chloride solution and stirred for 24 acetic anhydride ar h t d f5 hours to 35 9() C 5 hours at room temperature, and the mass whichprecip- The reaction mixture is then introduced into 200 ml of isPurififid y repreciplt'fltion from Water/10 l0 strength aqueous sodiumchloride solution and is Strength Sodium chloride SolutlOn/Charcoal- T fy stirred for 24 hours at room tem t Th d t ff stuff obtained dyesfabrics of polyacrylonitrile in violet which precipitates is filteredoff, washed with 5 d strength aqueous sodium chloride solution and driedin 10 It is probably a mixture corresponding to the formuvacuo at 45C.The resulting dyestuff of the formula lae C I 1113 H3 CH I CH- Q -11 G-0C H 01 I CH -CH OH dyes fabrics of polyacrylonitrile in violet-redshades of (m3 high fastness to light and to wet processing.

O H EXAMPLE 17 3 2 5 --CH-GH- -l( C1 6 g of the reaction productobtained in Example 1 are I I H heated with 3-formyl-N ethylcarbazole ina mixture of l 2 5 50 ml of glacial acetic acid and 1.5 ml of aceticanhy- Q Z' Q dride for 7 hours to 90C. The reaction mixture is pouredinto 200 ml of 10 strength aqueous sodium um chloride solution andstirred for 24 hours. The crude 3O dyestuff of the formula 3 3 -/2 s 01I hon-O l H c11 nowap-cn-on -o.

Cl 40 If the starting components'listed in Table 2 below are used forthe condensation and the instructions-given in i I I t c 11 Examplesl4-l7 are followed, dyestuffs are obtained 5 2" 2 J which dye fabrics ofpolyacrylonitrile in the colour shades indicated.

Table 2.

Carbonyl Component v Oxazoloindole Derivative Colour shade4-dimethylaminobenzaldehyde according to Example 1 brilliantbluish-tinged red Z-methylN-ethyl-N-B-chlorodo. clear bluish-tinged redethylaminobenzaldehyde 4-(N-methyl-N-B-cyanoethyl)-aminodo. rosebenzaldehyde 3Tormyl-N-ethylcarbazole according to Example 4 red3-formyl-N-ethylcarbazole according to Example 5 scarlet4-(N-methyl-N-Bcyanoethyl)-aminodo. bluish-tinged red benzaldehyde 3formyl-N-ethylcarbazole according to Example 7 brilliant red4-diethylaminobenzaldehyde do. violet 3-formyl-N-ethylcarbazoleaccording to Example 9 red 4-diethylaminobenzaldehyde according toExample 10 violet 4-(N-methyl-N-B-cyanoethyl)-aminoaccording to Example11 red-violet benzaldehyde which precipitates is reprecipitated fromwater/5 7 EXAMPLE strength sodium chloride solution. It is obtained as Aixt re of 4.1 g of the product obtained according greenishglisteningcrystals and dyes fabrics of polyt E l 1 d 3,2 g f 2- h 1i d-3- ld h d acl'ylomtrlle luminous Scarlet fed Shadesin a mixture of 20ml of glacial acetic acid and l g of 0 EXAMPLE l8 acetic anhydride iskept at .for 12 hours. The reaction mixture is introduced into 200 ml ofwater and the 3.1 g of thereactionproduct obtained in Example 7 dyestuffis gradually precipitated by adding 20 g of soand L9 g ofdiethylammobenzaldehyde in a mixture of dium chloride and purified byreprecipitation from water/sodium chloride solution in the presence ofcharcoal.

The dyestuff obtained, of the formula I L ca ca oa dyes fabrics ofpolyacrylonitrile in orange-coloured shades.

ter/sodium chloride solution. The dyestuff obtained corresponds to theformula I CH m -P I clca-cn-cn=c I I 1 1O CH2-CH2-0H I CH3 g l J anddyes fabrics of polyacrylonitrile in bluish-tinged red shades.

If the starting components listed in the table which follows are usedfor the condensation, and the procedure indicated in Example l7 isfollowed, dyestuffs are obtained which dye fabrics of polyacrylonitrilein the colour shades indicated.

If the starting components listed in the table which follows are usedfor the condensation and the procedure indicated in Example 19 isfollowed, dyestuffs are obtained which dye materials ofpolyacrylonitrile in the colour shades indicated.

lndole Derivative Oxazoloindole Derivative Colour shade2-methylindo|e-3-aldehyde 2-methylindole-3'aldehyde2-methylindole-3-aldehyde 2methylindole-3-aldehyde l.2dimethylindole-3-aldehyde 2 p-to|ylindole 3-aldehyde2-p-tolylindole-3-aldehyde Z-p-tolylindole-3-aldehyde2-p-tolylindole-3-aldehyde according to Example 4 according to Example 9according to Example 8 according to Example 6 according to Example 7according to Example 1 according to Example 9 according to Example 4according to Example 7 orange bluish-tinged red orange orange orangeorange bluish-tinged red orange orange l-methyI-2-p-toIylindole-3-according to Example 9 aldehyde l-ethyl-2-methyl-6.7benzo indole3-aldehyde l-ethyl 2-methyl-6.7-benzoindole-B-aldehyde according toExample 1 according to Example 9 violet bluish-tinged red violetAldehyde Component Oxazoloindole Derivative Colour shade 5-chlorol ,3 .3-trimethyl-2-formylmethyleneindoline 1,3 ,3.5-tetramethyl-Z-formylmethyleneindoline S-nitro-l,3.3-trimethyl-2-formylmethyleneindoline S-nitro-l ,3,3trimethyl-2-formylmethyleneindoline S-carbomethoxyJ,3,3-trimethyl-2-formylmethyleneindolinel.3,3-trimethyl-2-formylmethyleneindoline S-chloro-l ,3,3-trimethyl-2formylmethyleneindoline 5-chloro-l.3,3-trimethyl-2-formylmethyleneindoline 5chloro-l,3,Ltrimethyl-Z-formylmethyleneindoline 5-chl0r0 l ,3,3-trimethyl-2formylmethyleneindolinel.3,3-trimethyl2formylmethyleneindolinel,3,3,5-tetramethyl-2-formylmethyleneindoline 5-methoxy-l,3,3-trimethyl2-formylmethyleneindoline -mthoxy-l,3,3-trimethyl-2-formylmethyleneindole ,33.S-tetramethyl-2-formylmethyleneindoline 33trimethyl-2-formylmethyleneindoline3,3-trimethyl-2-formylmethyleneindoline3,3-trimethyl-2-formylmethyleneindoline chloro-l ,3,3-trimethyl-2-formylindoline EXAMPLE 2.1 g of the substance obtainedaccording to Example 1 and 3.8 g ofl,3,3-trimethyl-Z-formylmethyleneindoline in 20 ml ofglacial acetic acidare heated to ll0for 5 hours. The reaction mixture is poured into 150 mlof 20 strength sodium chloride solution whilst stirring and the productis purified by reprecipitation from wa- I claim: 1. Hydrazone dyestuffof the formula 6. The basic dyestuff of claim 1 having the formula inwhich R and R are C -C -alkyl, chloromethyl, trifluoro- H methyl,B-chloroethyl, B-methoxyethyl, B-cyanoc 3 ethyl or B-dimethylaminoethyl;i c 2. The dyestuff of claim 1 in which n is 0, 1 or 2. 3 w 3. Thedyestuff of claim 1 in which R4 and R5 are hy- -if O CH SQZ drogen. CH

4. The ha ic dyestuff of claim 1 having the formula 2 2 i 7. A basicdyestuff of the formula CH I a f i J 3 7 i- CH- N- N ch oh so i 3 3 4 l5GH 2 0H3 Q CH N N O 1 6H chssc" GH -(31 0B 3 5. The basic dyestuff ofclaim 1 having the formula CH \y CH=N H- CH -c h (3H 2. 6 5 CH -CH OH 33O 8. A basic dycstuff of the formula t 4* C3 H C-C @if-CH 7CH 1 (M 80 IL GH CH Or-1 2 5

2. The dyestuff of claim 1 in which n is 0, 1 or
 2. 3. The dyestuff ofclaim 1 in which R4 and R5 are hydrogen.
 4. The basic dyestuff of claim1 having the formula
 5. The basic dyestuff of claim 1 having the formula6. The basic dyestuff of claim 1 having the formula
 7. A basic dyestuffof the formula
 8. A basic dyestuff of the formula